EP1519997B1 - Einkomponentiges klebmittel zur anwendung bei der holzverarbeitung - Google Patents

Einkomponentiges klebmittel zur anwendung bei der holzverarbeitung Download PDF

Info

Publication number
EP1519997B1
EP1519997B1 EP03763150A EP03763150A EP1519997B1 EP 1519997 B1 EP1519997 B1 EP 1519997B1 EP 03763150 A EP03763150 A EP 03763150A EP 03763150 A EP03763150 A EP 03763150A EP 1519997 B1 EP1519997 B1 EP 1519997B1
Authority
EP
European Patent Office
Prior art keywords
weight
composition
stage polymer
adhesive composition
stage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03763150A
Other languages
English (en)
French (fr)
Other versions
EP1519997A2 (de
Inventor
Nicholas C. Lehman
Scott W. Rhein
John T. Anderson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
HB Fuller Licensing and Financing Inc
Original Assignee
HB Fuller Licensing and Financing Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/191,768 external-priority patent/US20040003892A1/en
Application filed by HB Fuller Licensing and Financing Inc filed Critical HB Fuller Licensing and Financing Inc
Priority to SI200331249T priority Critical patent/SI1519997T1/sl
Publication of EP1519997A2 publication Critical patent/EP1519997A2/de
Application granted granted Critical
Publication of EP1519997B1 publication Critical patent/EP1519997B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • C08F263/04—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids on to polymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof

Definitions

  • the invention relates to a one-part woodworking adhesive composition.
  • Woodworking adhesive compositions often are supplied as two part systems. Usually at least two components of the system cannot be stored together because they tend to crosslink too quickly to be suitable for later use. As a result, the end user must combine the two parts of the system to prepare the adhesive composition. The additional steps required to combine and mix the components of the two part system tend to complicate and lengthen the manufacturing process. Two part adhesive systems also require the end user to mix two components together in specified ratios to obtain an adhesive composition with predetermined properties and performance characteristics. Performance problems can arise if the proper amount of each component is not used.
  • the woodworking industry has had a long-standing goal to develop a one part adhesive composition for use in bonding wood substrates that exhibits good stability and can pass industry standards. Available one part wood working adhesive compositions tend to lack sufficient water resistance for many applications.
  • a woodworking adhesive composition prepared by a two stage emulsion polymer process is disclosed in U.S. Patent Nos. 5,439,960 (Mudge et al. ) and 5,391,608 (Mudge et al. ).
  • the invention features a stable one part adhesive composition suitable for bonding wood substrates.
  • the invention features an adhesive composition that includes a) an emulsion including a multi-stage polymer including a first stage polymer having a Tg from -20°C to 90°C and including from about 0.5 % by weight to about 3 % by weight latent crosslinking monomer based on the first stage monomer weight, and a second stage polymer having a Tg from 40°C to 140°C, the second stage polymer being different from the first stage polymer, and b) formaldehyde-based crosslinking agent, and c) catalyst, the adhesive composition being capable of passing the DIN EN 204 Test Method, after having been stored in a sealed container at 23°C for at least 30 days.
  • the adhesive composition passes the WATT-91 Test Method. In some embodiments, the adhesive composition passes the WATT-91 Test Method after aging in a sealed container for at least 30 days at 23°C. In other embodiments, the adhesive composition passes the WATT-91 Test Method after aging in a sealed container for at least 2 months at 23°C. In another embodiment, the adhesive composition passes the DIN EN 204 Test Method after aging in a sealed container for at least 2 months at 23°C. In some embodiments, the adhesive composition passes the WATT-91 Test Method after aging in a sealed container for at least 6 months at 23°C. In other embodiments, the adhesive composition, after aging for at least 2 months at 23°C, passes the DIN EN 204 Test Method and the WATT-91 Test Method.
  • the adhesive composition after aging for at least 3 months at 23°C, passes the DIN EN 204 Test Method and the WATT-91 Test Method. In other embodiments, the adhesive composition, after aging for at least 6 months at 23°C, passes the DIN EN 204 Test Method and the WATT-91 Test Method.
  • the second stage polymer includes from about 0.1 % by weight to about 10 % by weight latent crosslinking monomer based on the second stage monomer weight.
  • the catalyst is an acid catalyst.
  • the catalyst is selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, p-toluene sulfonic acid, and combinations thereof.
  • the catalyst is a Lewis acid.
  • the catalyst is selected from the group consisting of aluminum chloride, iron chloride, zirconium oxychloride, chromic nitrate, chromic perchlorate, aluminum nitrate, iron nitrate and zinc nitrate.
  • the first stage polymer has a Tg from 0°C to 70°C. In other embodiments, the first stage polymer has a Tg from 20°C to 50°C. In some embodiments, the first stage polymer includes vinyl ester. In other embodiments, the first stage polymer includes vinyl acetate. In one embodiment, the first stage polymer further includes vinyl ester other than vinyl acetate. In another embodiment, the first stage polymer further includes vinyl ester of versatic acid.
  • the second stage polymer has a Tg from 60°C to 120°C. In other embodiments, the second stage polymer has a Tg from 80°C to 120°C. In another embodiment, the second stage polymer includes methyl methacrylate. In some embodiments, the second stage polymer includes styrene, acrylonitrile, vinyl pivalate, or a combination thereof.
  • the multi-stage polymer comprises from 0.5 % by weight to 60 % by weight second stage polymer based on the weight of the first-stage polymer. In other embodiments, the multi-stage polymer comprises from 1 % by weight to about 30 % by weight second stage polymer based on the weight of the first stage polymer. In some embodiments, the multi-stage polymer comprises from 1 % by weight to 10 % by weight second stage polymer based on the weight of the first-stage polymer.
  • the adhesive composition further includes coalescing agent, urea, alcohol, plasticizer, antifoam, filler, biocide, tackifier, fire retardant, thickener, preservative, or a combination thereof.
  • the first-stage polymer includes from about 1 % by weight to about 2.5 % by weight latent crosslinking monomer based on the first stage monomer weight. In other embodiments, the first-stage polymer includes from about 1 % by weight to about 2 % by weight latent crosslinking monomer based on the first stage monomer weight.
  • the formaldehyde-based crosslinking agent is selected from the group consisting of resorcinol formaldehyde, urea-formaldehyde, melamine-formaldehyde, phenol-formaldehyde, trimethylol phenol, acrylamide-formaldehyde adducts, and combinations thereof.
  • the composition includes from about 1 % by weight to about 10 % by weight formaldehyde-based crosslinking agent.
  • the adhesive composition further includes alcohol.
  • the invention features an article that includes a substrate, and an adhesive composition including the reaction product of a) an emulsion including a multi-stage polymer including a first stage polymer having a Tg from -20°C to 90°C and including from about 0.5 % by weight to about 3 % by weight latent crosslinking monomer based on the first stage monomer weight, and a second stage polymer having a Tg from 40°C to 140°C, the second stage polymer being different from the first stage polymer, b) formaldehyde-based crosslinking agent, and c) catalyst, the adhesive composition being capable of passing the DIN EN 204 Test Method.
  • the substrate includes wood.
  • the article includes a second substrate, the first substrate being bonded to the second substrate through the adhesive composition.
  • the invention features a method of bonding substrates, the method including a) contacting a first substrate with an adhesive composition described herein and b) contacting the adhesive composition with a second substrate.
  • the method further includes applying pressure to the substrate construction to bond the first substrate to the second substrate through the adhesive composition. In some embodiments, the method further includes applying heat to the substrate construction. In some embodiments, the method further includes applying radio frequency to the substrate construction.
  • the invention features a woodworking adhesive composition that can be formulated for use as a one part woodworking adhesive composition that exhibits good shelf life stability, forms a good bond to wood substrates, and maintains good adhesion in high humidity environments and at elevated temperatures.
  • T g or "glass transition temperature” means the temperature at which a polymer exhibits a phase change from glassy, brittle solid to a liquid.
  • T g as referred to herein is calculated using a Differential Scanning Calorimeter according to P. Peyser, Naval Research Laboratory, Washington, D.C., Polymer Handbook, Third Edition, Section VI, "Solid State Properties,” John Wiley & Sons, New York pp. 209-279 (1989 ).
  • polymer refers to homopolymers, copolymers, multipolymers and polymers in any form.
  • multi-stage polymer means a polymer that includes at least a first polymer formed in a first polymerization process and at least a second polymer, compositionally different from the first polymer, formed in a second polymerization process.
  • latent crosslinking monomer means a monomer that includes at least one reactive functional group that remains essentially intact during formation of the emulsion polymer and provides a reactive site on the emulsion polymer that can subsequently be reacted under different reaction conditions, e.g., elevated temperature or drying of the emulsion.
  • the adhesive composition includes an emulsion comprising a multi-stage polymer that includes a first stage polymer having a Tg of from -20°C to 90°C, and a second stage polymer that is different from the first stage polymer and that has a Tg of from 40°C to 140°C, latent crosslinking monomer, formaldehyde-based crosslinking agent, and catalyst.
  • the adhesive composition is well suited to woodworking and to bonding wood substrates.
  • the adhesive composition preferably exhibits at least 10 N/mm 2 when tested according to DIN EN-204 Durability Class D4, Conditioning Sequence 1, at least 4 N/mm 2 when tested according to the DIN EN-204 Durability Class D4, Conditioning Sequence 3, at least 4 N/mm 2 when tested according to the DIN EN-204 Durability Class D4, Conditioning Sequence 5, or a combination thereof.
  • the adhesive composition passes DIN EN-204 entitled, "Classification of Non-Structural Adhesives for Joining Wood and Wood-Based Panel Products," Durability Class D4, Conditioning Sequences 1, 3 and 5 (October 1991) (herein after referred to as "The DIN EN-204 Test Method").
  • composition can also be formulated to pass WATT 91 (Wood Adhesives Temperature Test) Test Method for Wood Adhesives for Non-Structural Applications, Determination of the Hot Tensile Strength of Lap Joints Test Method.
  • WATT 91 Wood Adhesives Temperature Test
  • the adhesive composition passes both the DIN EN-204 Test Method and the WATT-91 Test Method.
  • the adhesive composition also exhibits good storage stability such that it maintains adhesive bonding properties over its useful shelf life.
  • the adhesive composition preferably is free flowing (i.e., can be poured as is or can be poured after stirring) and remains free of coagulation (i.e., irreversible increase in viscosity rendering the composition incapable of being applied to a wood substrate) over its shelf life.
  • the adhesive composition is sufficiently stable to pass the DIN EN 204 test method, the WATT -91 test method or both over the shelf life of the composition, preferably after having been stored in a sealed container at 23°C for at least 30 days, more preferably for at least 2 months, more preferably for at least 3 months, most preferably for at least 6 months.
  • the multi-stage polymer of the adhesive composition is in the form of an emulsion polymer that includes at least two compositionally different polymers.
  • the polymers can be present in the emulsion in a variety of configurations. Useful methods of making multi-stage polymers are described in, e.g., U.S. Patent 3,562,235 and 3,787,522 .
  • a multi-stage polymer is a core-shell polymer that includes a polymer core and a second polymer disposed on the surface of the polymer core.
  • the emulsion polymer can be formulated such that the second polymer at least partially surrounds the polymer core. In other embodiments, the emulsion polymer can be formulated such that the second polymer completely surrounds the polymer core.
  • the multi-stage polymer can be prepared by various emulsion polymerization processes including, e.g., batch, semi-continuous and continuous emulsion polymerization processes. Examples of such procedures are described in U.S. Patent Nos. 5,439,960 , 2,754,280 , 2,795,564 , and 3,732,184 .
  • One example of a suitable two stage emulsion polymerization process includes a first stage in which a first stage polymer is prepared by emulsion polymerizing a vinyl monomer and a latent crosslinking monomer in the presence of a stabilizing agent to produce a stabilized polymer having a Tg from -20°C to 90°C, preferably from 0°C to 70°C, more preferably from 20°C to 50°C, and a second stage in which a second stage polymer is prepared by emulsion polymerizing a monomer having a Tg of at least 40°C (such monomers are often referred to as "hard monomers"), in the presence of the first stage monomer, and optionally in the presence of a latent crosslinking monomer, to produce a second stage polymer having a Tg from 40°C to 140°C, preferably from 60°C to 120°C, more preferably from 80°C to 120°C.
  • a stabilizing agent to produce a stabilized polymer having a
  • Suitable polymers for the first stage emulsion polymer include, e.g., homo- and copolymers of polyvinyl ester monomers and mixtures thereof.
  • Suitable fist stage vinyl ester monomers include, e.g., include vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl esters of saturated, branched monocarboxylic acids having from 9 to 10 carbon atoms in the acid radical, vinyl esters of long-chain (e.g., from 10 to 20 carbon atoms) branched and unbranched, saturated and unsaturated fatty acids (e.g., vinyl laurate, vinyl stearate, vinyl esters of benzoic acid, and substituted derivatives of benzoic acid (e.g., vinyl p-tert-butylbenzoate)) and combinations thereof.
  • Suitable vinyl ester monomers also include the vinyl esters of vinyl alcohol (i.e., versatic acid) available under the VEOVA series of trade designations from Shell Chemical Company (Houston, Texas) including VEOVA 5 vinyl ester of a 5 carbon neo-acid, VEOVA 9 vinyl ester of a 9 carbon neo-acid, VEOVA 10 vinyl ester of a 10 carbon neo-acid, and VEOVA 11 vinyl ester of an 11 carbon neo-acid.
  • VEOVA 5 vinyl ester of a 5 carbon neo-acid VEOVA 9 vinyl ester of a 9 carbon neo-acid
  • VEOVA 10 vinyl ester of a 10 carbon neo-acid VEOVA 11 vinyl ester of an 11 carbon neo-acid.
  • Useful first stage emulsion polymers include from about 5 % by weight to 100 % by weight vinyl ester, preferably from about 5 % by weight to about 40 % by weight vinyl ester, more preferably from 5 % by weight to 20 % by weight vinyl ester based on first stage polymer weight, and from 0 % by weight to 99 % by weight vinyl acetate, preferably from about 65 % by weight to about 95 % by weight vinyl acetate, more preferably from about 75 % by weight to about 95 % by weight vinyl acetate based on first stage polymer weight.
  • vinyl ester monomer including, e.g., other ethylenically unsaturated monomers that can be copolymerized with vinyl esters including, e.g., ⁇ , ⁇ -unsaturated acids including, e.g., acrylic acid, methacrylic acid and esters thereof with primary and secondary saturated, monohydric alcohols having from 1 to 18 carbon atoms, e.g., methanol, ethanol, propanol, butanol, 2-ethylhexyl alcohol, cycloaliphatic alcohols and relative long chain (e.g., from 10 to 20 carbon atoms) fatty alcohols (e.g., stearyl alcohol and lauryl alcohol), a, ⁇ -unsaturated dicarboxylic acids including, e.g., maleic acid, fumaric acid, itaconic acid, and citraconic acid, mono- and diesters thereof with saturated monohydric, aliphatic alcohols having
  • suitable comonomers for the first stage emulsion polymer include ethylenically unsaturated hydrocarbons including, e.g., ethylene and a-olefins having form 3 to 18 carbon atoms including, e.g., propylene and butylene, styrene, vinyltoluene, vinylxylene, and halogenated, unsaturated, aliphatic hydrocarbons including, e.g., vinyl chloride, vinyl fluoride, vinylidene chloride and vinylidene fluoride.
  • These monomers can be present in the polymer in an amount of no greater than 50 % by weight, preferably from 0.1 % by weight to about 25 % by weight based on the first stage monomer weight.
  • the latent crosslinking monomer present in the first stage emulsion is a crosslinking monomer that includes reactive groups that are available for activation after the multi-stage emulsion polymer is formed.
  • suitable latent crosslinking monomers include acrylamide, n-methyl acrylamide, isobutyl methoxy acrylamide, N-alkylolamides of alpha, beta ethylenically unsaturated carboxylic acids having 3-10 carbons, such as N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacrylamide, methylol acrylamidoglycolate methyl ether, N-ethanol methacrylamide, N-methylol maleamide, N-methylol maleamide, N-methylol maleamic acid, N-methylol maleamic acid esters, the N-alkylol amides of the vinyl aromatic acids, such as N-methylol-p-vinylbenzamide; N-(
  • the amount of latent crosslinking monomer present the in the first stage emulsion polymer is from about 0.1 % by weight to about 3 % by weight, preferably from about 0.5 % by weight to about 2 % by weight, more preferably from about 1 % by weight to about 2 % by weight based on the first stage monomer weight.
  • the first stage emulsion polymerization is carried out in the presence of a stabilizing agent (i.e., an agent capable of stabilizing the emulsion).
  • a stabilizing agent i.e., an agent capable of stabilizing the emulsion.
  • suitable stabilizing agents include protective colloids and surfactants.
  • suitable protective colloids include polyvinyl alcohol, polyvinyl ethers, polysaccharides including, e.g., hydroxyethyl cellulose, carboxymethylcellulose, carboxymethyl starch, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyvinylpyrrolidone, polycarboxylic acids (e.g., polyacrylic acid), copolymers of maleic acid or maleic anhydride, and combinations thereof.
  • the protective colloid when present, preferably is present in the first stage emulsion in an amount of from 0.5 % by weight to about 15 % by weight, preferably from about 1 % by weight to about 10 % by weight based on the first stage monomer weight.
  • Suitable nonionic surfactants include alkylphenoxypolyethoxyethanols having alkyl groups of about 7 to 18 carbon atoms and 10 to 60 or more oxyethylene units including, e.g., octylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, and dodecylphenoxypolyethoxyethanols, ethylene oxide derivatives of long chained carboxylic acids including, e.g., lauric, myristic, palmitic, oleic, and stearic acid, containing 10 to 60 oxyethylene units per molecule, ethylene oxide condensates of long-chained alcohols including, e.g., octyl, decyl, lauryl, stearyl and cetyl alcohols, ethylene oxide derivatives of etherified or
  • Suitable anionic surfactants include higher fatty alcohol sulfates including, e.g., sodium lauryl sulfate, alkylaryl sulfonates (e.g., sodium salt of t-octylphenyl sulfonate, the sodium dioctyl sulfosuccinates, and disodium fatty alkyl alkanolamide sulfosuccinate), and the ammonium salt of a sulfate or phosphate ester of an alkylphenoxy poly(ethyleneoxy) ethanol, where the oxyethylene content is from 3 to 30 moles per alkylphenol.
  • higher fatty alcohol sulfates including, e.g., sodium lauryl sulfate, alkylaryl sulfonates (e.g., sodium salt of t-octylphenyl sulfonate, the sodium dioctyl sulfosuccinates, and diso
  • Suitable cationic surfactants include, e.g., N-dodecyl trimethyl ammonium chloride, and N-vinyl benzyl trimethyl ammonium chloride.
  • the surfactant can be present in the first stage emulsion in an amount of from 0 % by weight to about 10 % by weight, more particularly from about 1 % by weight to about 6 % by weight based on the first stage monomer weight.
  • the emulsion polymerization process for forming the second stage emulsion polymer occurs in the presence of the first stage emulsion polymer.
  • Useful second stage monomers for forming the second stage emulsion polymer include monomers having a Tg from 40°C to 140°C, preferably from 60°C to 120°C, more preferably from 80°C to about 120°C.
  • Suitable second stage monomers include methyl methacrylate, styrene, acrylonitrile, vinyl pivalate, copolymers of methyl methacrylate C 2 -C 4 methacrylates (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate), and combinations thereof
  • the emulsion polymer of the second stage includes from about 0.5 % by weight to about 100 % by weight methyl methacrylate, more preferably from about 50 % by weight to about 100 % by weight methyl methacrylate, more preferably from about 75 % by weight to about 100 % by weight methyl methacrylate.
  • the amount of second stage polymer in the multi-stage emulsion polymer is from about 0.5 % by weight to about 60 % by weight, preferably from about 1 % by weight to about 15 % by weight, more preferably from about 1 % by weight to about 10 % by weight based upon the first stage monomer weight.
  • Latent crosslinking monomers suitable for use in the second stage emulsion polymerization process include the latent crosslinking monomers set forth above and incorporated herein.
  • the latent crosslinking monomer is preferably present in the second stage emulsion polymer in an amount of from about 0.1 % by weight to about 10 % by weight, preferably from about 0.5 % by weight to about 5 % by weight, more preferably from about 0.5 % by weight to about 2 % by weight based on the second stage monomer weight.
  • the multi-stage polymer can also include other comonomers including, e.g., polyethylenically unsaturated monomers, monomers having N-functional groups, hydroxy-functional monomers, and combinations thereof.
  • Suitable polyethylenically unsaturated monomers include, e.g., diallyl phthalate, diallyl maleate, triallyl cyanurate, tetraallyloxyethane, divinylbenzne, butanediol 1, 4-dimethacrylate, triethylene glycol dimethacrylate, divinyl adipate, allyl(meth)acrylate, vinyl crotonate, methylenebisacrylamide, hexanediol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, and combinations thereof.
  • the amount of polyethylenically unsaturated monomer present in the polymer is preferably no greater than 10 % by weight, more preferably from about 0.01 to about 2 % by weight based on the second stage monomer weight.
  • Suitable monomers having N-functional groups include, e.g., allyl carbamate, acrylonitrile, N-methylolallyl carbamate N-vinylformamide, N-vinylpyrrolidone, and combinations thereof.
  • the amount of monomers having N-functional groups present in the polymer is preferably no greater than 15 % by weight, more preferably from about 0.01 % by weight to about 10 % by weight based on the second stage monomer weight.
  • Suitable hydroxy-functional monomers include, e.g., hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate and adducts thereof with ethylene oxide, propylene oxide and combinations thereof.
  • the amount of hydroxy-functional monomer present in the emulsion polymer preferably is no greater than 25 % by weight, more preferably from about 0.01 to about 15 % by weight based on the second stage monomer weight.
  • Useful formaldehyde-based crosslinking agents include, e.g., resorcinol formaldehyde, urea-formaldehyde, melamine-formaldehyde, phenolics including, e.g., phenol-formaldehyde and trimethylol phenol, and acrylamide-formaldehyde adducts and combinations thereof.
  • Useful formaldehyde-based crosslinking agents are available from a variety of commercial suppliers including, e.g., Ashland Specialty Chemical Company (Dublin, Ohio), Borden Chemical, Inc. (Columbus, Ohio), Cytec Inc. (West Paterson, New Jersey), and Georgia-Pacific Corporation (Atlanta, Georgia)
  • the amount of formaldehyde-based crosslinking agent present in the adhesive composition is from about 0.1 % by weight to about 10 % by weight, more preferably from about 1 % by weight to about 6 % by weight, most preferably from about 2 % by weight to about 4 % by weight based on the weight of the adhesive composition.
  • strong acid catalysts including, e.g., organic acids, inorganic acids and Lewis acids.
  • Suitable strong acid catalysts include, e.g., aluminum chloride, iron chloride, zirconium oxychloride, chromic nitrate, chromic perchlorate, aluminum nitrate, iron nitrate, zinc nitrate, hydrochloric acid, sulfuric acid, phosphoric acid, and paratoluene sulfonic acid, and combinations thereof.
  • the catalyst is present in the adhesive composition in an amount of from about 0.1 % by weight to about 6 % by weight, preferably from about 1 % by weight to about 5 % by weight, more preferably from about 1 % by weight to about 4 % by weight based on the weight of the adhesive composition.
  • the adhesive composition can optionally include a coalescing agent, which assists in coalescing the emulsion polymer particles.
  • suitable coalescing agents include butyl carbitol acetate (i.e., diethylene glycol monobutyl ether acetate), glycol ethers, ether alcohols including, e.g., mono alkyl ether alcohols including, e.g., diethylene glycol C 1-6 mono- or dialkyl ethers, diethylene glycol ethyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol ethyl ether, propylene glycol ethyl ether, glycol ether, triethylene glycol ethyl ether, isobutyrate, benzyl alcohol, 3-methoxybutanol-1, monomethyl, monoethyl and monobutyl ethers of diethylene glycol, triethylene glycol, dipropylene glycol and tripropy
  • a coalescing agent is present in the adhesive composition, it is preferably present in the adhesive composition in an amount of no greater than about 5 % by weight, preferably from about 0.1 % by weight to about 3 % by weight, more preferably from about 0.5 % by weight to about 1.5 % by weight based on the weight of the adhesive composition.
  • the adhesive composition can optionally include alcohol. Suitable alcohols include, e.g., isopropanol, methanol, and ethanol, and combinations thereof. If alcohol is present in the composition, it is preferably present in an amount of from about 0.1 % by weight to about 5 % by weight, more preferably from about 0.1 % by weight to about 3 % by weight, more preferably from about 0.5 % by weight to about 1.5 % by weight based on the weight of the adhesive composition.
  • alcohol include, e.g., isopropanol, methanol, and ethanol, and combinations thereof. If alcohol is present in the composition, it is preferably present in an amount of from about 0.1 % by weight to about 5 % by weight, more preferably from about 0.1 % by weight to about 3 % by weight, more preferably from about 0.5 % by weight to about 1.5 % by weight based on the weight of the adhesive composition.
  • the adhesive composition may also include other additives including, e.g., plasticizers, antifoams, fillers, biocides, tackifiers, fire retardants, thickeners, preservatives, and combinations thereof.
  • additives including, e.g., plasticizers, antifoams, fillers, biocides, tackifiers, fire retardants, thickeners, preservatives, and combinations thereof.
  • the adhesive composition is formulated to exhibit an acidic pH, preferably a pH from 2 to 6, more preferably a pH from 2.5 to 4.
  • the adhesive composition can be used to bond a variety of substrates including, e.g., wood, e.g., solid wood substrates, particle board, fiber board, chip board, hard board, oriented strand board, plywood, laminates, other cellulose-based substrates including, e.g., paper, and combinations thereof.
  • substrates including, e.g., wood, e.g., solid wood substrates, particle board, fiber board, chip board, hard board, oriented strand board, plywood, laminates, other cellulose-based substrates including, e.g., paper, and combinations thereof.
  • the substrates can be bonded to each other through the adhesive composition according to a variety of mechanisms and processes including, e.g., pressure (e.g., cold clamp and hot press), heat, radio frequency curing, and combinations thereof.
  • pressure e.g., cold clamp and hot press
  • heat e.g., heat, radio frequency curing, and combinations thereof.
  • Test procedures used in the examples include the following.
  • the durability of the adhesive bond formed between two wood substrates is determined according to DIN EN-204 entitled, "Classification Of Non-Structural Adhesives For Joining Wood And Wood-Based Panel Products," Durability Class D4, Conditioning Sequences 1, 3 and 5 (October 1991).
  • the samples are prepared according to European Standard EN 205 (1991).
  • the composition passes the DIN EN-204 test method if it achieves a value of at least 10.0 N/mm 2 under Conditioning Sequence 1, at least 4.0 N/mm 2 under Conditioning Sequence 3, and at least 4.0 N/mm 2 under Conditioning Sequence 5.
  • the durability of the adhesive bond formed between two wood substrates is determined according to the WATT 91 (Wood Adhesives Temperature Test) Test Method for Wood Adhesives for Non-Structural Applications, Determination of the Hot Tensile Strength of Lap Joints Test Method.
  • the composition passes the WATT-91 test method if it achieves a value of at least 7.0 N/mm 2 .
  • Stage 1 The first stage polymer emulsion was prepared by adding the following components to a glass reactor equipped with a water bath for heating and cooling, an agitator, a condenser and appropriate feed apparatus: 20.8 parts of deionized water, 1.7 parts 92 % hydrolyzed polyvinyl alcohol, 1.1 parts 88 % hydrolyzed polyvinyl alcohol, 0.04 parts buffer and 0.04 parts defoamer. The reactor was heated until the polyvinyl alcohol was fully dissolved and then the temperature adjusted to 65°C.
  • the polymerization was initiated with the addition of 10.6 parts vinyl acetate, 4.5 parts VEOVA 10 vinyl ester of a 10 carbon neo-acid (Shell Chemical Company, Houston, Texas), 0.46 parts N-methylolacrylamide, 0.06 parts dioctyl ester of sodium sulfosuccinic acid (Cytec Inc., West Paterson, NJ) and 0.5 parts water in which 0.02 parts ammonium persulfate and 0.02 parts diammonium phosphate had been dissolved.
  • the water bath was used to control the temperature so that the polymerization proceeded from 68°C to 85°C over the feed additions.
  • Stage 2 After completion of the first stage, the reactor temperature was adjusted to 75°C and 2.12 parts methyl methacrylate, 0.04 parts N-methylolacrylamide and 1.5 parts water were added.
  • the second stage polymerization was initiated with the addition of 0.01 parts tert-butyl hydroperoxide and 0.08 parts sodium formaldehyde sulfoxylate rinsed in with 0.44 parts water.
  • the reactor contents were held for thirty minutes in the temperature range of 70°C to 75°C and then a second and optionally third addition of tert-hydroperoxide and sodium formaldehyde sulfoxylate was added. The reactor contents were then cooled forming the two-stage emulsion polymer.
  • Example 1 contained 51.5 % solids and had a Brookfield viscosity 8900 cps measured on a Brookfield viscometer using spindle number 6 at 20 rotations per minute (rpm). The composition of Example 1, after aging at room temperature for four months, was visually inspected and found to be free flowing and free of coagulation.
  • Example 2 The composition of Example 2 was prepared following the process of Example 1 with the exception that the total amount of N-methylolacrylamide added in Stage 1 was 1.12 parts.
  • Example 2 passed DIN EN 204, Durability Class D4, Conditioning Sequences 1 and 3.
  • Example 3 was prepared following the process of Example 1 with the exception that the total amount of N-methylolacrylamide added in Stage 1 was 1.78 parts.
  • Example 3 passed the Watt-91 Test Method.
  • Example 4 was prepared following the process of Example 1 with the exception that the Shell VEOVA 9 was used instead of VEOVA 10 in Stage-1 and 3.2 parts of methyl methacrylate and no N-methylolacrylamide were used in Stage-2.
  • Example 4 passed DIN EN 204 Durability Class D4 Conditioning Sequence 5 and the Watt-91 Test Method.
  • Example 5 The composition of Example 5 was prepared following the process of Example 1 with the exception that 3.4 parts 50% aluminum chloride hexahydrate solution (32° Baume) was added during the compounding step.
  • Example 5 passed DIN EN 204 Durability Class D4, Conditioning Sequences 3 and 5.
  • Example 6 The composition of Example 6 was prepared following the process of Example 1 with the exception that 1.65 parts hydroxyethyl cellulose was used instead of 2.8 parts polyvinyl alcohol, 9.0 parts VEOVA 9 and 6.1 parts vinyl acetate were added in the induction step of Stage-1, and 3.2 parts of methyl methacrylate and 0.07 parts N-methylolacrylamide were used in Stage 2.
  • Example 6 passed DIN EN 204 Durability Class D4, Conditioning Sequence 5 and the Watt-91 Test Method.
  • Example 7 was prepared following the process of Example 1 and then stored in a sealed container for two weeks at 95°F, which was the equivalent of aging for six months at room temperature.
  • Example 7 The aged composition of Example 7 was visually inspected and found to be free flowing and free of coagulation.
  • the composition of Example 7 also passed DIN EN 204 Durability Class D4 Conditioning Sequence 5 and the WATT-91 Test Method.
  • Example 8 The composition of Example 8 was prepared following the process of Example 1 and then the composition was stored at 120°F for two weeks, which was the equivalent of aging for one year at room temperature.
  • Example 8 The aged composition of Example 8 was visually inspected and found to be free flowing and free of coagulation.
  • the composition of Example 8 also passed DIN EN 204 Durability Class D4 Conditioning Sequence 5 and the WATT-91 Test Method.
  • Example 9 The composition of Example 9 was prepared following the process of Example 2 and then the composition was store in a sealed container for two weeks at 95°F, which was the equivalent of aging for six months at room temperature.
  • Example 9 The aged composition of Example 9 was visually inspected and found to be free flowing and free of coagulation.
  • the composition of Example 9 also passed DIN EN 204 Durability Class D4 Conditioning Sequences 3 and 5 and the WATT-91 Test Method.
  • Example 2 when stored at room temperature for four months was found upon visual inspection to be free flowing and free of coagulation.
  • Example 1 The adhesive composition of Example 1 was tested according to the WATT-91 Test Method and passed.
  • Example 3 The adhesive composition of Example 3 was tested in accordance with the DIN EN 204 Test Method Durability Class D4 Conditioning Sequences 1, 3 and 5 and passed.
  • Example 5 The adhesive composition of Example 5 was tested in accordance with the WATT-91 Test Method and passed.
  • Example 1 The adhesive composition of Example 1, was tested in accordance with DIN EN 204 Test Method Durability Class D4 Conditioning Sequences 1, 3 and 5 and passed.
  • Example 3 The adhesive composition of Example 3 was inspected after having been stored in a sealed container at room temperature for four months and found to be free flowing and free of coagulation
  • Example 2 The adhesive composition of Example 2 was tested in accordance with the WATT-91 Test Method and passed.
  • the first stage polymer emulsion was prepared by adding the following components to a glass reactor equipped with a water bath for heating and cooling, an agitator, a condenser and appropriate feed apparatus: 25.0 parts of deionized water, 0.45 parts 88 % hydrolysis polyvinyl alcohol, 1.13 parts CELLOSIZE QP-300 buffer (Dow Chemical Co, Midland, Michigan) and defoamer.
  • the reactor was heated until the polyvinyl alcohol was fully dissolved and then the temperature was adjusted to 65°C.
  • the polymerization was initiated with the addition of 10.6 parts vinyl acetate, 4.5 parts VEOVA 10 vinyl ester of a 10 carbon neo-acid (Shell Chemical Company Houston, Texas), 0.80 parts N-methylolacrylamide, 0.06 parts dioctyl ester of sodium sulfosuccinic acid (Cytec West Paterson, New Jersey) and 0.5 parts water in which 0.02 parts ammonium persulfate and 0.02 parts diammonium phosphate had been dissolved.
  • the water bath was used to control the temperature so that the polymerization proceeded from 68°C to 85°C over the feed additions.
  • the first stage reaction was complete after the temperature peaked and began to fall.
  • the reactor temperature was adjusted to 75°C and 2.12 parts methyl methacrylate, 0.04 parts N-methylolacrylamide and 1.5 parts water were added.
  • the second stage polymerization was initiated with the addition of 0.01 parts tert-butyl hydroperoxide and 0.08 parts sodium formaldehyde sulfoxylate rinsed in with 0.44 parts water.
  • the reactor contents were held for thirty minutes in the temperature range of 70°C to 75°C and then a second addition of tert-hydroperoxide and sodium formaldehyde sulfoxylate was added.
  • the reactor contents were then cooled forming the two-stage emulsion polymer.
  • Example 17 passed DIN EN 204 Test Method, Durability Class D4, Conditioning Sequences 1, 3 and 5, and Watt-91 Test Method.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (23)

  1. Eine einkomponentige Klebemittelzusammensetzung zur Holzbearbeitung umfassend:
    a) eine Emulsion umfassend ein mehrstufiges Polymer umfassend ein Polymer der ersten Stufe, das eine Tg von -20 °C bis 90 °C besitzt und umfassend von ungefähr 0,5 Gew.-% bis ungefähr 3 Gew.-% latentes quervernetzendes Monomer, bezogen auf das Gewicht des Monomers der ersten Stufe, und
    ein Polymer der zweiten Stufe, das eine Tg von 40 °C bis 140 °C besitzt, wobei das Polymer der zweiten Stufe sich von dem Polymer der ersten Stufe unterscheidet;
    b) Formaldehyd-basierendes quervernetzendes Mittel; und
    c) Katalysator,
    wobei die Klebemittelzusammensetzung geeignet ist, das DIN EN 204 Testverfahren zu bestehen, nachdem sie in einem versiegelten Behälter bei 23 °C für mindestens 30 Tage gelagert wurde.
  2. Die Klebemittelzusammensetzung gemäß Anspruch 1, wobei die Klebemittelzusammensetzung das WATT-91 Testverfahren und das DIN EN 204 Testverfahren nach Alterung in einem versiegelten Behälter für mindestens 30 Tage bei 23 °C besteht.
  3. Die Klebemittelzusammensetzung gemäß Anspruch 1, wobei die Klebemittelzusammensetzung mindestens eines der Testverfahren WATT-91 und DIN EN 204 nach Alterung in einem versiegelten Behälter für mindestens 2 Monate bei 23 °C besteht.
  4. Die Zusammensetzung gemäß Anspruch 1, wobei die Klebemittelzusammensetzung mindestens eines der Testverfahren WATT-91 und DIN EN 204 nach Alterung in einem versiegelten Behälter für mindestens 3 Monate bei 23 °C besteht.
  5. Die Zusammensetzung gemäß Anspruch 1, wobei die Klebemittelzusammensetzung mindestens eines der Testverfahren WATT-91 und DIN EN 204 nach Alterung in einem versiegelten Behälter für mindestens 6 Monate bei 23 °C besteht.
  6. Die Klebemittelzusammensetzung gemäß irgendeinem der Ansprüche 1 - 5,
    wobei das Polymer der zweiten Stufe von ungefähr 0,1 Gew.-% bis ungefähr 10 Gew.-% latentes quervernetzendes Monomer, bezogen auf das Gewicht des Monomers der zweiten Stufe, umfasst.
  7. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 6, wobei der Katalysator ausgewählt ist aus der Gruppe bestehend aus Salzsäure, Schwefelsäure, Phosphorsäure, p-Toluolsulfonsäure, Aluminiumchlorid, Eisenchlorid, Zirkoniumoxychlorid, Chromnitrat, Chromperchlorat, Aluminiumnitrat, Eisennitrat, und Zinknitrat, und Kombinationen davon.
  8. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 7, wobei das Polymer der ersten Stufe eine Tg von 20 °C bis 50 °C besitzt.
  9. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 8, wobei das Polymer der ersten Stufe Vinylester umfasst.
  10. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 8, wobei das Polymer der ersten Stufe Vinylacetat umfasst.
  11. Die Zusammensetzung gemäß Anspruch 10, wobei das Polymer der ersten Stufe ferner Vinylester der Versatic-Säure umfasst.
  12. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 11, wobei das Polymer der zweiten Stufe eine Tg von 60 °C bis 120 °C besitzt.
  13. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 11, wobei das Polymer der zweiten Stufe eine Tg von 80 °C bis 120 °C besitzt.
  14. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 13, wobei das Polymer der zweiten Stufe Methylmethacrylat, Styrol, Acrylnitril, Vinylpivalat, oder eine Kombination davon umfasst.
  15. Die Klebemittelzusammensetzung gemäß irgendeinem der Ansprüche 1 - 14,
    wobei das mehrstufige Polymer von 1 Gew.-% bis ungefähr 30 Gew.-% Polymer der zweiten Stufe, bezogen auf das Gewicht des Polymers der ersten Stufe umfasst.
  16. Die Klebemittelzusammensetzung gemäß irgendeinem der Ansprüche 1-14,
    wobei das mehrstufige Polymer von 1 Gew.-% bis 10 Gew.-% Polymer der zweiten Stufe, bezogen auf das Gewicht des Polymers der ersten Stufe umfasst.
  17. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 16, wobei das Polymer der ersten Stufe von ungefähr 1 Gew.-% bis ungefähr 2,5 Gew.-% latentes quervernetzendes Monomer, bezogen auf das Gewicht des Monomers der ersten Stufe umfasst.
  18. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 17, umfassend von ungefähr 1 Gew.-% bis ungefähr 10 Gew.-% Formaldehyd-basierendes quervernetzendes Mittel.
  19. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 18, wobei das Formaldehyd-basierende quervernetzende Mittel ausgewählt ist aus der Gruppe bestehend aus Resorzinolformaldehyd, Harnstoff-Formaldehyd, Melamin-Formaldehyd, Phenol-Formaldehyd, Trimethylolphenol, Acrylamid-Formaldehydaddukte, und Kombinationen davon.
  20. Die Zusammensetzung gemäß irgendeinem der Ansprüche 1 - 19, ferner umfassend Alkohol.
  21. Ein Verfahren zum Kleben von Substraten, wobei das Verfahren umfasst:
    a) Kontaktieren eines ersten Substrats mit der einkomponentigen Klebemittelzusammensetzung zur Holzbearbeitung gemäß Anspruch 1; und
    b) Kontaktieren der Klebemittelzusammensetzung mit einem zweiten Substrat.
  22. Das Verfahren gemäß Anspruch 21, ferner umfassend die Anwendung von Hitze auf die Substratkonstruktion, um das erste Substrat durch die Klebemittelzusammensetzung an das zweite Substrat zu binden.
  23. Das Verfahren gemäß Anspruch 21, ferner umfassend die Anwendung von Radiofrequenz auf die Substratkonstruktion.
EP03763150A 2002-07-08 2003-07-01 Einkomponentiges klebmittel zur anwendung bei der holzverarbeitung Expired - Lifetime EP1519997B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
SI200331249T SI1519997T1 (sl) 2002-07-08 2003-07-01 Enokomponentni adhezivni sestavek za obdelavo lesa

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US10/191,768 US20040003892A1 (en) 2002-07-08 2002-07-08 One part woodworking adhesive composition
US191768 2002-07-08
US259114 2002-09-26
US10/259,114 US6872278B2 (en) 2002-07-08 2002-09-26 One part woodworking adhesive composition
PCT/US2003/020930 WO2004005417A2 (en) 2002-07-08 2003-07-01 One-part woodworking adhesive composition

Publications (2)

Publication Number Publication Date
EP1519997A2 EP1519997A2 (de) 2005-04-06
EP1519997B1 true EP1519997B1 (de) 2008-05-07

Family

ID=30117811

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03763150A Expired - Lifetime EP1519997B1 (de) 2002-07-08 2003-07-01 Einkomponentiges klebmittel zur anwendung bei der holzverarbeitung

Country Status (11)

Country Link
EP (1) EP1519997B1 (de)
CN (1) CN1281701C (de)
AT (1) ATE394457T1 (de)
AU (1) AU2003247768A1 (de)
BR (1) BRPI0311464B1 (de)
CA (1) CA2488103C (de)
DE (1) DE60320794D1 (de)
NZ (1) NZ536842A (de)
PL (1) PL215233B1 (de)
RU (1) RU2308473C2 (de)
WO (1) WO2004005417A2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2361642T3 (es) * 2008-06-23 2011-06-20 Wacker Chemie Ag Dispersión polimérica en emulsión resistente al calor.
EP2585502A1 (de) * 2010-06-25 2013-05-01 Celanese Emulsions GmbH Weichgemachte vinylacetat-copolymerbinderzusammensetzungen für eine faserschnittmatte
CN105504148B (zh) * 2016-02-25 2017-07-28 广州晶海化工有限公司 一种水性压敏胶及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4948822A (en) * 1989-02-27 1990-08-14 National Starch And Chemical Investment Holding Corporation Laminating adhesives
US5391608A (en) * 1989-04-26 1995-02-21 National Starch And Chemical Investment Holding Corporation Woodworking adhesives based on multistage emulsion polymer
ES2397505T3 (es) * 2000-07-07 2013-03-07 Wacker Chemical Corporation Composición de látex polimérico basado en acetato de vinilo, especialmente para adhesivos

Also Published As

Publication number Publication date
WO2004005417A2 (en) 2004-01-15
WO2004005417A3 (en) 2004-03-04
PL373047A1 (en) 2005-08-08
ATE394457T1 (de) 2008-05-15
CN1281701C (zh) 2006-10-25
RU2308473C2 (ru) 2007-10-20
AU2003247768A1 (en) 2004-01-23
CN1665901A (zh) 2005-09-07
DE60320794D1 (de) 2008-06-19
BR0311464A (pt) 2005-03-29
EP1519997A2 (de) 2005-04-06
RU2005102936A (ru) 2005-07-10
CA2488103C (en) 2012-06-05
NZ536842A (en) 2007-01-26
CA2488103A1 (en) 2004-01-15
PL215233B1 (pl) 2013-11-29
BRPI0311464B1 (pt) 2015-08-04

Similar Documents

Publication Publication Date Title
EP1505085B1 (de) Wasserresistente Klebstoffe, Verfahren zu deren Herstellung und deren Verwendung
US5296532A (en) Adhesive compositions containing aqueous copolymer dispersions and acid metal salts or free acids
JP4121097B2 (ja) 乳化重合を開始するためのレドックス触媒系
US6730722B1 (en) Cross-linkable polymer powder compositions
DE19962566A1 (de) Verfahren zur Herstellung von Vinylester-(Meth)acrylsäureester-Mischpolymeri- saten
US6872278B2 (en) One part woodworking adhesive composition
EP1792922A1 (de) Schutzkolloidstabilisiertes Dispersionspulver
US20050250899A1 (en) Use of copolymers stabilized with a protective colloid in cement-free or low-cement coating materials
US5391608A (en) Woodworking adhesives based on multistage emulsion polymer
US6730718B1 (en) Discoloration-fast dispersion adhesives having a prolonged potlife
EP1519997B1 (de) Einkomponentiges klebmittel zur anwendung bei der holzverarbeitung
DE102012209210A1 (de) Vinylacetat-Copolymere für hydraulisch abbindende Baustoffmassen
EP0394774B1 (de) Holzbearbeitungsklebstoffe auf der Basis von Mehrstufen-Emulsionspolymeren
US6890975B2 (en) Water-redispersible polymer powders for building adhesive compositions
US6616798B2 (en) Process for preparing adhesives having improved adhesion
US20020032268A1 (en) Process for preparing polymer dispersions with a high solids content
US6489391B1 (en) Process for preparing aqueous, protective colloid stabilized vinyl ester homopolymer and copolymer dispersions
DE102010042003A1 (de) Verwendung von Polypropylenoxid oder Ethylenoxid-Propylenoxid-Mischpolymerisat als haftungsverbessernden Zusatz in Klebe- und Armierungsmörtel
CA2260488A1 (en) Water-resistant adhesive based on a vinyl actate emulsion polymer containing a nonionic polyurethane
EP4157804A1 (de) Verfahren zur herstellung von in wasser redispergierbaren polymerpulvern für baustofftrockenformulierungen
WO2001049788A1 (de) Polymerdispersion mit vernetzerharz, deren herstellung und verwendung
JP2666406B2 (ja) 水分散型樹脂粉末組成物の製造法
DE10225444A1 (de) Mehrkomponentenklebstoff
PL194046B1 (pl) Sposób wytwarzania stabilizowanych koloidami ochronnymi polimerów estrów winylowych i polimerów estrów winylowych - etylen w postaci ich wodnych dyspersji oraz zastosowanie wodnych dyspersji polimerów wytworzonych tym sposobem
RU2267505C2 (ru) Дисперсия полимера с сшивающей смолой, ее получение и применение

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041228

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20060317

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEHMAN, NICHOLAS, C.

Inventor name: ANDERSON, JOHN, T.

Inventor name: RHEIN, SCOTT, W.

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ANDERSON, JOHN, T.

Inventor name: LEHMAN, NICHOLAS, C.

Inventor name: RHEIN, SCOTT, W.

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REF Corresponds to:

Ref document number: 60320794

Country of ref document: DE

Date of ref document: 20080619

Kind code of ref document: P

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20080620

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: MAIWALD PATENTANWALTSGESELLSCHAFT (SCHWEIZ) MBH

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2305510

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: HU

Ref legal event code: AG4A

Ref document number: E003787

Country of ref document: HU

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080731

26N No opposition filed

Effective date: 20090210

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080807

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080701

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: H.B. FULLER LICENSING & FINANCING, INC.

Free format text: H.B. FULLER LICENSING & FINANCING, INC.#1200 WILLOW LAKE BOULEVARD, BOX 64683#SAINT PAUL, MINNESOTA 55164-0683 (US) -TRANSFER TO- H.B. FULLER LICENSING & FINANCING, INC.#1200 WILLOW LAKE BOULEVARD, BOX 64683#SAINT PAUL, MINNESOTA 55164-0683 (US)

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080808

REG Reference to a national code

Ref country code: EE

Ref legal event code: GB1A

Ref document number: E002341

Country of ref document: EE

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20110728 AND 20110803

REG Reference to a national code

Ref country code: HU

Ref legal event code: GB9C

Owner name: H.B. FULLER COMPANY, US

Free format text: FORMER OWNER(S): H.B. FULLER LICENSING & FINANCING, INC., US

Ref country code: HU

Ref legal event code: FH1C

Free format text: FORMER REPRESENTATIVE(S): FRANKNE DR. MACHYTKA DAISY, GOEDOELLE, KEKES, MESZAROS & SZABO SZABADALMI ES VEDJEGY IRODA, HU

Representative=s name: GOEDOELLE, KEKES, MESZAROS & SZABO SZABADALMI , HU

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG

Ref country code: CH

Ref legal event code: PUE

Owner name: H. B. FULLER COMPANY

Free format text: H.B. FULLER LICENSING & FINANCING, INC.#1200 WILLOW LAKE BOULEVARD, BOX 64683#SAINT PAUL, MINNESOTA 55164-0683 (US) -TRANSFER TO- H. B. FULLER COMPANY#1200 WILLOW LAKE BLVD. P.O. BOX 64683#ST. PAUL MINNESOTA 55164-0683 (US)

REG Reference to a national code

Ref country code: PT

Ref legal event code: PC4A

Owner name: H.B. FULLER COMPANY, US

Effective date: 20110729

REG Reference to a national code

Ref country code: NL

Ref legal event code: SD

Effective date: 20110916

REG Reference to a national code

Ref country code: SI

Ref legal event code: SP73

Owner name: H.B. FULLER COMPANY; US

Effective date: 20110922

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20110725

Year of fee payment: 9

Ref country code: DK

Payment date: 20110725

Year of fee payment: 9

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: H.B. FULLER COMPANY, US

Effective date: 20111026

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60320794

Country of ref document: DE

Representative=s name: MAIWALD PATENTANWALTSGESELLSCHAFT MBH, DE

REG Reference to a national code

Ref country code: SK

Ref legal event code: PC4A

Ref document number: E 3839

Country of ref document: SK

Owner name: H.B. FULLER COMPANY, ST. PAUL, MINNESOTA, US

Free format text: FORMER OWNER: H.B. FULLER LICENSING & FINANCING, INC., SAINT PAUL, MINNESOTA, US

Effective date: 20100401

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 60320794

Country of ref document: DE

Representative=s name: MAIWALD PATENTANWALTSGESELLSCHAFT MBH, DE

Effective date: 20120102

Ref country code: DE

Ref legal event code: R081

Ref document number: 60320794

Country of ref document: DE

Owner name: H.B. FULLER COMPANY, ST. PAUL, US

Free format text: FORMER OWNER: H.B. FULLER LICENSING & FINANCING, INC., SAINT PAUL, MINN., US

Effective date: 20120102

Ref country code: DE

Ref legal event code: R082

Ref document number: 60320794

Country of ref document: DE

Representative=s name: MAIWALD PATENTANWALTS- UND RECHTSANWALTSGESELL, DE

Effective date: 20120102

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: EE

Payment date: 20120621

Year of fee payment: 10

Ref country code: CZ

Payment date: 20120621

Year of fee payment: 10

Ref country code: SK

Payment date: 20120621

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20120801

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20120727

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SI

Payment date: 20120627

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120731

Year of fee payment: 10

Ref country code: IT

Payment date: 20120723

Year of fee payment: 10

Ref country code: BE

Payment date: 20120725

Year of fee payment: 10

Ref country code: ES

Payment date: 20120726

Year of fee payment: 10

Ref country code: HU

Payment date: 20120626

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20120102

Year of fee payment: 10

Ref country code: NL

Payment date: 20120724

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20120620

Year of fee payment: 10

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20140102

BERE Be: lapsed

Owner name: H.B. FULLER COMP

Effective date: 20130731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20140201

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Effective date: 20130731

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 394457

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130701

REG Reference to a national code

Ref country code: SI

Ref legal event code: KO00

Effective date: 20140205

REG Reference to a national code

Ref country code: SK

Ref legal event code: MM4A

Ref document number: E 3839

Country of ref document: SK

Effective date: 20130701

REG Reference to a national code

Ref country code: EE

Ref legal event code: MM4A

Ref document number: E002341

Country of ref document: EE

Effective date: 20130731

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

Ref country code: SK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140201

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

Ref country code: HU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130702

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130702

Ref country code: EE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

Ref country code: SI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130702

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20120625

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140102

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130731

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20150709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130702

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: RO

Payment date: 20190624

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20190719

Year of fee payment: 17

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20200701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200701

Ref country code: RO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200701

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20220721

Year of fee payment: 20

Ref country code: DE

Payment date: 20220620

Year of fee payment: 20

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230424

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60320794

Country of ref document: DE